RESUMO
Capacity fading as a function of lithiation/delithiation cycles is a major limitation of Li-ion batteries. Most Li storage materials are susceptible to this phenomenon due to the degradation of the crystal structure and particle integrity as a result of volume changes associated with lithiation/delithiation processes and/or irreversible redox reactions. However, some Li storage materials show an increase in capacity with an increase in cycles; this phenomenon has been termed "negative fading." Negative fading in Li host materials is usually associated with the additional charge storage at the particle/solid-electrolyte interface (SEI) layer, decomposition/formation of the SEI layer, or redox reactions of various Li species at the interface. In this work, we report the observation of negative fading in a newly discovered anode material, TiNbO4 (TNO), and reveal amorphization as a new mechanism for negative fading in Li host materials. This assertion was confirmed via a close relationship between changes in the crystal structure and the Li storage mechanism in TNO. Given that other titanium niobium oxide analogues (e.g., TiNb2O7) suffer from capacity loss due to amorphization, this unique electrochemical behavior of TNO may provide an interesting new direction to tune the titanium niobium oxides for high-performance, stable battery anodes.
RESUMO
The limited capacity of graphite anodes in high-performance batteries has led to considerable interest in alternative materials in recent years. Due to its high capacity, titanium niobium oxide (TiNb2O7, TNO) with a Wadsley-Roth crystallographic sheared structure holds great promise as a next-generation anode material, but a comprehensive understanding of TNO's electrochemical behavior is lacking. In particular, the mechanism responsible for the capacity fading of TNO remains poorly elucidated. Given its metastable nature (as an entropy-stabilized oxide) and the large volume change in TNO upon lithiation and delithiation, which has long been overlooked, the factors governing capacity fading warrant investigation. Our studies reveal that the structural weakness of TNO is fatal to the long-term cycling stability of TNO and that the capacity fading of TNO is driven by amorphization, which results in a significant increase in impedance. While nanostructuring can kinetically boost lithium intercalation, this benefit comes at the expense of capacity fading. Carbon doping in TNO can effectively suppress the critical impedance increase despite the amorphization, providing a possible remedy to the stability issue.
RESUMO
Despite the enormous attention paid to cobalt oxide materials as efficient water splitting electrocatalysts, a deep understanding of their activity discrepancy is still elusive. In this work, we showed that stabilization of the internally generated oxygen evolution reaction (OER) active phase (oxyhydroxide) is crucial for ZnCo2O4 electrocatalysts. A systematic evaluation of the bulk and nanostructured ZnCo2O4 system concomitant with nanostructured Co3O4 showed that leaching of Zn is the driving force behind the near-surface transformation to the oxyhydroxide phase. The relative contribution to this near-surface reconstruction was found to be surface-sensitive. The electrochemical observations combined with Raman and impedance spectroscopy revealed that the good catalytic activity could be attributed to the formation of the cobalt oxyhydroxide phase, which was created by the dissolution of Zn from the nanostructured surface. Moreover, this study sheds light on previous contradicting postulates regarding the discrepancy of the OER activity of ZnCo2O4. Our finding regarding the formation of the OER active phase in spinel Zn-Co oxide will motivate researchers to focus more on the near-surface reconstruction behavior of cobalt-based oxide electrocatalysts in the future.
